WO2013102938A1 - Compositions de polypropylène modifié pour assurer un étranglement réduit dans des processus de coulage de feuille mince par extrusion ou de revêtement par extrusion - Google Patents

Compositions de polypropylène modifié pour assurer un étranglement réduit dans des processus de coulage de feuille mince par extrusion ou de revêtement par extrusion Download PDF

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WO2013102938A1
WO2013102938A1 PCT/IN2013/000012 IN2013000012W WO2013102938A1 WO 2013102938 A1 WO2013102938 A1 WO 2013102938A1 IN 2013000012 W IN2013000012 W IN 2013000012W WO 2013102938 A1 WO2013102938 A1 WO 2013102938A1
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modified polypropylene
polypropylene
composition according
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WO2013102938A8 (fr
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Kalyani Suresh CHIKHALIKAR
Ashish Kishore LELE
Harshwardhan Vinayak POL
Kishor Shankar JADHAV
Sunil janardan MAHAJAN
Zubair AHMAD
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Council Of Scientific & Industrial Research
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Priority to US14/370,830 priority Critical patent/US10081720B2/en
Priority to EP13706743.5A priority patent/EP2800764B1/fr
Publication of WO2013102938A1 publication Critical patent/WO2013102938A1/fr
Publication of WO2013102938A8 publication Critical patent/WO2013102938A8/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5393—Phosphonous compounds, e.g. R—P(OR')2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/105—Esters; Ether-esters of monocarboxylic acids with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/10—Chemical modification of a polymer including a reactive processing step which leads, inter alia, to morphological and/or rheological modifications, e.g. visbreaking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates

Definitions

  • the present invention relates to a composition of polyolefin for reducing the extent of film/coating necking of polypropylene in extrusion processes.
  • the present invention provides polypropylene (PP) compositions modified with long chain branch of polypropylene (LCB-PP) to reduce necking in extrusion film casting or extrusion coating processes.
  • PP polypropylene
  • LCB-PP long chain branch of polypropylene
  • composition of polypropylene shows higher flow activation energy, and sensitivity of viscosity to temperature, and good stretchability.
  • Polypropylene (PP) films are coated on raffia fabric in industrial extrusion film casting/coating processes. Casting of film is also the first step in a BOPP process.
  • PP a linear polymer, exhibits shear thinning and extensional thinning properties. Consequently, PP displays significant reduction in the width of the final film/coating in an extrusion film casting or coating process. This is called the 'necking' defect.
  • the processor is left with a film/coating having significantly reduced width as compared to the original die width. Necking also causes the film to thicken at the edges, which is called ' edge-beading' .
  • film edges are typically trimmed, which further reduces the usable width of the film.
  • the uneven thickness leads to differential shrinkage resulting in delamination.
  • the problem/need is to reduce the extent of necking and the consequent edge-beading of extruded film/coating for polypropylene.
  • US 2012/20730 discloses the high melt strength polypropylene (HMS-PP) functionalized maleated polypropylene.
  • the nanolayer enhancement of biaxially oriented polypropylene film for increased gas barrier is disclosed in Polymer 51 (24), 2010, 5807-5814 by Yijian Lin et al.
  • CN101381491 relates to a method for preparing a polypropylene compound with high beta crystal content, comprising of polypropylene resin, an antioxidant and an amide nucleating agent.
  • compositions with PP and multi functional acrylate monomers are disclosed in prior arts and possess several properties of industrial application, it is also well known that such combinations cause formation of undesirable side products, such as homo polymers of acrylates. Such side products are known to reduce the purity of the desired polymer product.
  • the constraint regarding the necking and subsequent edge-beading is not addressed, which is an important industrial problem, affecting the quality of film produced in the casting process.
  • the object of this invention is to provide a composition of polypropylene that exhibits significantly reduced necking tendency and higher flow activation energy.
  • Another object of the invention is to provide a composition of polypropylene devoid of acrylates that exhibits significantly reduced necking tendency and higher flow activation energy.
  • BOPP Biaxially oriented polypropylene
  • LDPE Low-density polyethylene
  • LCB-PP Long chain branch of polypropylene
  • MFR/MFI Melt flow rate or index
  • the present invention provides a modified polypropylene composition
  • a modified polypropylene composition comprising long chain branch of polypropylene; free radical initiator; primary antioxidant; secondary anti ⁇ oxidant; acid neutralizer, characterized in that the flow activation energy of the composition is in the range of 40-60 kj/mole.
  • the polypropylene is impact copolymer (ICP) having a density range from 0.9 to 0.95 g/cm3 and the melt flow rate or index of impact copolymer (ICP), is in the range from 0.5 to 2.5 g/10 min.
  • ICP impact copolymer
  • free radical initiator may be selected from the group consisting of peroxidicarbonates of formula R' -OCOOCO-R, wherein R and R' are identical or different and independently selected from branched or linear (C1-C5) alkyl, (C6 ⁇ C12) alicyclic, cetyl, [3-(isobutyryloxy)-2,2,4-trimethylpentyl]; in the range of 2000-8000 ppm by wt. preferably 4000-6000ppm by wt.
  • said primary antioxidant is hindered phenolic-type antioxidants selected from the group Pentaerythritol Tetrakis(3-(3,5-di-tert- butyl-4-hydroxyphenyl)propionate); IRGANOX 1010 FF; IRGANOX 1010 DD; l,3,5-tris(3,5- di-tert-butyl-4-hydroxybenzyl)-l,3,5-triazine-2,4,6(lH,3H,5H)-trione.and l,3,5Trimethyl2,4,6tris(3,5di-tert-butyl-4hydroxybenzyl)benzene 330. in the range of 200 - 800 ppm by weight, preferably 400 to 800 ppm.
  • the secondary oxidant may be organo phosphites or organo phosphonite, selected from Tris (2,4-di-tert-butylphenyl)phosphate,Bis (2,4-di-t-butylphenyl) Pentaerythritol Diphosphite, ULTRANOX 627A, 2,4,6tri-t- butylphenyl-2-butyl-2-ethyl- 1 , 3-propanediolphosphite , Bis (2 ,4-dicumylphenyl) pentaerythritol diphosphite, tris[2-[[2,4,8,10-tetra-tert- butyldibenzo[d,f][l ,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine,[4-[4-bis(2,4-ditert- butylphenoxy)phosphanyl
  • an acid neutralizer is metal salt
  • the metal is selected from the group consisting of alkali, an alkaline-earth or transition-metal, preferably the metal is selected from Na, K, Ca, Zn ,A1 and like thereof, while the metal salt can be carbonate, stearate, hydroxide, acetate, oxide, alkoxide or combination thereof in the range of 200-1000 ppm by wt., preferably 300-900 ppm by wt.
  • Still another embodiment of the invention wherein the increase in die swell is in the range of 50-100%.
  • the present invention provides a composition of polypropylene (PP) with long chain branch of polypropylene (LCB-PP) to reduce necking and edge-beading defect, wherein the modified polypropylene composition comprising of a) long chain branch of polypropylene b) free radical initiator; c)primary antioxidant; d) secondary antioxidant; e) acid neutralizer.
  • the instant modified polypropylene composition shows higher flow activation energy, greater sensitivity of viscosity to temperature and improved strechabillity.
  • Figure 1 is a plot of complex viscosity. Ml shows higher complex viscosity and shear thinning against unmodified impact copolymer.
  • Fig 2 Extensional viscosity plot for ICP base copolymer at different strain rates. ICP is a linear copolymer and hence does not show strain hardening.
  • Fig 3 Extensional viscosity plot for Ml modified copolymer at different strain rates. Ml show strain hardening which is an indication of presence of long chain branching inside modified copolymer.
  • Figure 4 depicts schematic for extrusion film casting.
  • Figure 5 depicts normalized width of film (ratio of width of the film after it comes out of the die to width of the die) as a function of the draw ratio (defined as tangential velocity of chill roll to exit velocity at film die) to study neck-in tendency of unmodified impact PP(ICP) and Ml (A) materials in extrusion film casting.
  • the figure shows the reduced necking of the modified polymer composition(A) as against the unmodified impact co polymer(ICP).
  • the present invention provides a composition of polypropylene (PP) with long chain branch of polypropylene (LCB-PP) to reduce necking and edge-beading defect, wherein the modified polypropylene composition comprising of a)long chain branch of polypropylene b) free radical initiator; c)primary antioxidant; d) secondary antioxidant; e) acid neutralizer.
  • the instant modified polypropylene composition shows higher flow activation energy, greater sensitivity of viscosity to temperature and improved stretchability.
  • the present invention provides a composition of polypropylene (PP) with long chain branch of polypropylene (LCB-PP) to reduce necking and edge-beading defect, wherein the modified polypropylene composition comprising of a)long chain branch ofpolypropylene b) free radical initiator; c) primary antioxidant; d) secondary antioxidant; e) acid neutralizer.
  • PP polypropylene
  • LCB-PP long chain branch of polypropylene
  • the polypropylene can be a homopolymer, a random copolymer, an impact copolymer, a blend or mixture of any of these, or a blend of a modified homopolymer with a second phase, i.e., 1.5 Melt flow index polypropylene (MFI PP) Impact copolymer.
  • MFI PP Melt flow index polypropylene
  • the polypropylene can be isotactic or syndiotactic, with a melt flow index or rate (MFI) of from 0.1 to 5 g/10 min, preferably 0.5 to 2.5 g/10 min.
  • MFI melt flow index or rate
  • Melt Flow Index is the output rate (flow) of the mass of polymer in grammes that occurs in 10 minutes through a standard die, which is measured according to ASTM D 1238 standard at 230° C. under a load of 2.16 kg.
  • the polypropylene used in the instant composition is impact copolymer (ICP), wherein the ICP having a density range from 0.9-0.95g/cm 3 ,
  • the ICP may have a melting point of 230° C and a melt flow rate or index (MFR) ranging from 1 to 2 g/10 min.
  • the composition of PP is Modified copolymer A (Modified PP-A composition), which comprises;
  • the free radical initiator is selected from the compounds of peroxidicarbonates family of general formula R' -OCOOCO-R, and having half-life in the range 0.1 - 1 min at the extrusion temperature of PP.
  • the free radical initiator is selected from the group of peroxidicarbonates.
  • the peroxidicarbonates having general formula R' -OCOOCO-R wherein R and R' are free radicals which may be identical or different and independently selected from branched or linear (C1-C5) alkyl, (C6-C12) alicyclic, cetyl, [3-(isobutyryloxy)-2,2,4-trimethylpentyl];
  • the initiator consisting of peroxydicarbonates group may be present in a reaction mixture in an amount ranging from 3000 ppm to 6000 ppm by wt. , particularly 4000-6000 ppm by wt., based on the total weight of the final PP. composition; whereas initiator consisting of dialkyl peroxide group may be present in a reaction mixture in an amount ranging from 100 to 2000 ppm by wt., particularly 100-1000 ppm, based on the total weight of the final PP composition.
  • the modification of neat Polypropylene is done in a reactive extrusion process in a single or twin screw extruder having residence time in the range of the half -life of the initiator.
  • the instant PP composition may display a reduced melt pressure due to the presence of long chain branching, which results in a higher extrusion rate when compared to neat polypropylene with similar melt flow rate.
  • the primary antioxidants involved in the invention may include hindered phenolic-type antioxidants selected from the group Pentaerythritol Tetrakis(3-(3,5-di-tert-butyl-4- hydroxyphenyDpropionate); IRGANOX 1010 FF; IRGANOX 1010 DD; l,3,5-tris(3,5-di-tert- butyl-4-hydroxybenzyl)- 1 , 3 , 5-triazine-2 , 4, 6(1 H , 3H , 5H)-trione.
  • Such antioxidant provides long-term thermal stability to the instant PP composition. While higher amounts of these primary antioxidants may be used, whereas the quantity is in the range of 200 to 800 ppm by weight, preferably 400 to 800 ppm.
  • the secondary antioxidants may include organo phosphites or organo phosphonite, such as Tris (2,4-di-tert-butylphenyl)phosphate,Bis (2,4-di-t-butylphenyl) Pentaerythritol Diphosphite, ULTRANOX 627A, 2,4,6tri-t-butylphenyl-2-butyl-2-ethyl-l,3- propanediolphosphite,Bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tris[2-[[2,4,8,10- tetra-tert-butyldibenzo[d,f][l,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine,[4-[4-bis(2,4-ditert butylphenoxy)phosphanylphenyl]phenyl]-bis(2,4-
  • secondary antioxidants comprises the benzofuranone (lactone) derivatives or thioesters of fatty acids, wherein these secondary antioxidants function as processing stabilizers by providing stability in melt flow and color during the melt processing of the polymer material also it enhance the heat aging stability of primary antioxidants.
  • the amount of secondary antioxidants is comparatively higher than primary anti-oxidant, wherein the quantity is in the range of 400 -1400 ppm by weight, preferably 500 to 1200 ppm by wt.
  • Acid neutralizers used for the present invention can be metal salts, wherein metal is selected from the group consisting of alkali, an alkaline-earth or transition-metal particularly the metal is selected from Na, K, Ca, Zn ,A1 and like thereof, while the metal salt can be carbonate, stearate, hydroxide, acetate, oxide, alkoxide or combination thereof.
  • the acid neutralizers used in the present composition may be in the range of 200-1000 ppm by wt., particularly 300-900 ppm by wt.
  • the invention provides method of making modified-PP which includes reactively blending of long chain branch of polypropylene, with free radical initiator, primary anti-oxidant, secondary antioxidant and acid neutralizer, in a twin extruder with Length to diameter ratio L/D of the screws in the range of 22-25 to obtain modified polypropylene product with reduced necking.
  • the PP composition of the invention provides extensional strain-hardening ability to the base PP which leads to enhancement of the ability of PP to withstand the planar extensional stresses during extrusion film casting.
  • the PP composition of the invention provides long relaxation times which contributes to higher resistance to stretching and thereby increases the ability of PP to withstand the planar extensional stresses during extrusion film casting.
  • the PP composition shows higher flow activation energy (Table 2) which leads to greater sensitivity of viscosity to temperature, accordingly improves the stretchability during cooling of the film in a casting process.
  • the flow activation energy of modified PP-composition is in the range of 40-60 (kj/mole)
  • LCB-PP is a shear thinning material (figure 1), which significantly attributes advantage in melt processing in an extruder. Higher activation energy, zero shear viscosity, longer relaxation time, more shear-thinning and increased elasticity in shear rheology results are strong indications of presence of long chain branching in modified copolymers. Strain hardening in extensional viscosity for modified copolymers is also strong indication of presence of branching; same is poor in base copolymer.
  • the composition of polypropylene (PP) modified with long chain branch of PP reduce the necking up to 50% (Figure 5).
  • peroxide modified copolymer (modified PP-A) shows considerably decreased neck-in tendency in an extrusion film casting process, because peroxide modified composition shows higher zero shear viscosity, greater shear-thinning and larger elongational strain-hardening in rheology results and base copolymer shows poor strain hardening ( Figures 1, 2 and 3).
  • modified polypropylene film made by the instant composition is transparent or translucent and retains stretchability.
  • the modified compositions were studied for increase in die swell.
  • Die swell is measured as the ratio of extrudate diameter to die diameter.
  • modified compositions As polymer melt leaves the die, it expands due to relaxation of stresses at the die exit and extrudate diameter increases as compared to die diameter.
  • the modified compositions indicating presence of long chain branching and in turn increase in elasticity, swell more as compared to unmodified composition. This is measured in same capillary rheometer in which MFI is measured. Extrudate diameter is measured and ratio of extrudate diameter to die diameter is taken and percentage is calculated.
  • increase in die swell is desired in the range of 50-100%. This is evident from die swell result as enlisted in table 2.
  • the increase in die swell for the modified compositions of the invention is in the range of 50-100%.
  • an article can be obtained by subjecting the modified-PP composition to a extrusion film coating or casting process, alternatively foaming, sheet extrusion thermoforming,
  • the modified polypropylene composition may be useful in food packaging, office supplies, structural supports, laminate compositions, polymeric foam substrate, decorative surfaces, outdoor furniture, point-of-purchase signs and displays, house wares and consumer goods, building insulation, ' cosmetics packaging, outdoor replacement materials, lids and food/beverage containers, appliances, utensils, electronic components, automotive parts, enclosures, medical supplies, glass and metal containers, toys, piping, also applicable in magazine covers, clothes packaging, agriculture packaging, construction packaging, bags and pouches, gift wraps and baskets, lamination/protective films, floristry packing consumer products, including diaper backing, garment bags, household wrap and trash bags, materials handling, including stretch wrap and shrink wrap and like thereof. Additionally, the advantages gained with polyolefin films, particularly polypropylene films are ease of processing, light weight, good toughness and tear resistance, flexibility, chemical resistance and relatively low cost compared with other plastics.
  • polypropylene-based films can be co-extruded with various other polymers, including ethylene vinyl alcohol (EVOH), Ionomer, linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE) nylon, polyamide/ethylene-vinyl acetate (PA/EVA), polyester barrier resins and adhesive tie layers to produce multilayer films with special, high-performance properties for large scale applications.
  • EVOH ethylene vinyl alcohol
  • Ionomer linear low-density polyethylene
  • HDPE high-density polyethylene
  • PA/EVA polyamide/ethylene-vinyl acetate
  • polyester barrier resins polyamide/ethylene-vinyl acetate
  • Extrusion Film Casting Extrusion film casting experiments were performed on a 19 mmD single screw extruder (SSE) (Thermo Haake Polylab System) equipped with a film die of 100 mm width x 0.45 mm lip thickness and chill roll attachment. Extrusion was done at 20 rpm screw speed, chill roll speeds of 50 to 850 rpm and at take up length of 228mm. Temperature profile of extruder is shown in table below:
  • the single screw extrusion temperature at 20 rpm screw speed is in the range of 150° C- 200° C.
  • the following examples, which include preferred embodiments, will serve to illustrate the practice of this invention, it being understood that the particulars shown are by way of examples and for purpose of illustrative discussion of preferred embodiments of the invention only and are not limiting the scope of the invention.
  • the 1.5 MFI PP impact copolymer was mixed with 5000 ppm by wt. of dicetyl peroxydicarbonate and primary antioxidant Irgonox 1010 in the quantity of 500 ppm by wt. and secondary antioxidant PEPQ with 600 ppm by wt. Further the composition was blended with 600 ppm by wt. of calcium stearate, to obtain modified PP-A.
  • Primary Antioxidant-lrganox 1010 Pentaerythritol Tetrakis(3-(3,5-di-tert-butyl-4 hydroxyphenyOpropionate)

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

La présente invention concerne une composition de polypropylène modifié qui présente une énergie d'activation de l'écoulement supérieure et un étranglement réduit dans la formation d'un film/d'un revêtement par extrusion, ladite composition comprenant une ramification à longue chaîne de polypropylène, un initiateur de radicaux libres, un antioxydant primaire, un antioxydant secondaire, un neutraliseur par acide, éventuellement un monomère multifonctionnel. En outre, la composition de polypropylène présente une sensibilité supérieure de la viscosité à la température, ainsi qu'une meilleure aptitude à l'étirage.
PCT/IN2013/000012 2012-01-07 2013-01-07 Compositions de polypropylène modifié pour assurer un étranglement réduit dans des processus de coulage de feuille mince par extrusion ou de revêtement par extrusion WO2013102938A1 (fr)

Priority Applications (2)

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US14/370,830 US10081720B2 (en) 2012-01-07 2013-01-07 Modified polypropylene compositions for reduced necking in extrusion film casting or extrusion coating processes
EP13706743.5A EP2800764B1 (fr) 2012-01-07 2013-01-07 Compositions de polypropylène modifié pour assurer un étranglement réduit dans des processus de coulage de feuille mince par extrusion ou de revêtement par extrusion

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IN3532DE2011 2012-01-07
IN3532/DEL/2011 2012-01-07

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EP3409701A1 (fr) 2017-05-31 2018-12-05 Borealis AG Composition de polymère de propylène réticulable
KR20190063122A (ko) * 2017-11-29 2019-06-07 롯데케미칼 주식회사 과산화물을 이용한 변성폴리올레핀 제조방법

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US20180126697A1 (en) 2015-08-13 2018-05-10 Exxonmobil Chemical Patents Inc. Multi-Layered Sheets Comprising a High Melt Strength Polypropylene
WO2018147944A1 (fr) 2017-02-07 2018-08-16 Exxonmobil Chemical Patents Inc. Polypropylènes à haute résistance à l'état fondu présentant une aptitude au traitement améliorée
CN110248995A (zh) 2017-02-07 2019-09-17 埃克森美孚化学专利公司 具有改进的加工性的高熔体强度聚丙烯
CN111051365B (zh) 2017-07-13 2023-05-23 埃克森美孚化学专利公司 应变硬化聚丙烯的制备方法
CN109810411B (zh) * 2019-01-29 2021-10-22 北京工商大学 提高β成核剂制备β晶型长链支化聚丙烯时的成核效率的方法
US11286317B2 (en) * 2019-04-12 2022-03-29 Indian Oil Corporation Limited Morphology modified heterophase propylene copolymers and their products thereof
KR20210007679A (ko) * 2019-07-12 2021-01-20 현대자동차주식회사 정전용량형 압력센서 및 그 제조방법과 정전용량형 압력센서 장치

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EP2800764B1 (fr) 2017-05-31

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